Blow molding

ABSTRACT

This invention relates to method and means for controlling the material distribution of a plastic parison during extrusion by a control system used to vary the opening of the extrusion outlet.

United States Patent [72] Inventors Kenneth C. Petersen. Scotia:

Thomas M. Galklewlcz. Schenectady. both of New York [21] Appl. No. 46,545 [22) Filed June 15.1970

[45 I Patented Nov. 2, 1971 Continuation-impart of application Ser. No. 873.059, Oct. 31. 1969. This application June 15. imfser. No. 46,545

[73] Assignee Schenectady Chemicals. Inc..

Schenectady. New York [54] HIGH TEMPERATURE RESISTANT POLYCIILOROPRENE ADHESIVE RESIN 19 Claims. No Drawings [52] US. Cl 260/25. 27. 845. 846 (30835122 [5]] Int. Cl

" s01 FieldoiSearch 260/25. 27.845.846

I I References Cited UNITED STATES PATENTS 2.938.876 5/1960 Monis 260/25 3.198.760 8/1965 Widenour 260/25 Primary Examiner-Hosea E. Taylor Assistant Examiner-William E. Parker Attorney-Cushman. Darby. and Cushman ABSTRACT: Superior polychloroprene adhesives are prepared by incorporating the reaction product of an alkali catalyzed alkyl phenol-formaldehyde resin and zinc resinate.

Preferably an arylphenol and/or bisphenol A is also incorporated. Also preferably rosin is included in the composition.

Other zinc compounds. e.g. zinc oxide. zinc borate. zinc phosphate. zinc carbonate. and zinc salicylate can be used in place of zinc resinate.

HIGH TEMPERATURE RESISTANT POLYCHLOROPRENE ADHESIVE RESIN This application is a continuation in part of Application 873.059 filed October 31. 1969. now abandoned.

The present invention relates to neoprene adhesives.

lt is an object of the invention to improve the properties of neoprene adhesives.

"Another object is to increase the peel and shear stress resistance of neoprene adhesives at elevated temperatures.

Still further objects and the entire scope of applicability of the present invention will become apparent from the de tailed description given hereinafter; it should be understood. however. that the detailed description and specific examples. while indicating preferred embodiments of the invention. are given by way of illustration only. since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

it has now been found that these objects can be attained by preparing an adhesive cement containing pol ychloroprene (neoprene) and the reaction product of an alkali catalyzed alkylphenol and/or arylphenol formaldehyde resin and zinc resinate. Rosin is preferably added as a processing aid and does not interfere with the excellent high temperature adhesion developed in neoprene adhesives utilizing the zinc resinate modified alkylphenol-formaldehyde resin of the present invention. There is also preferably employed a chlorophenol or arylphenol. e.g. p-phenylphenol. p-tolyphenol or alpha methyl styryl phenol and/or Bisphenol A as modifiers for the alkylphenol. The aryl phenol can be used by itself without an alkylphenol.

The alkylphenol is preferably a para substituted phenol in which the substituent is an alkyl group of 2 to 6 carbon atoms. The para substituted phenol is preferably pt-butyl phenol but there can be employed p-t-amyl phenol. p-hexyl phenol. p-n-butyl phenol. p-cyclohexyl phenol. p-ethyl phenol. p-isopropyl phenol.

It has further been found that in place of zinc resinate in preparing the resins for incorporation into polychloroprene adhesives there can be used other zinc compounds such as zinc oxide. zinc carbonate. zinc borate. zinc salicylate and zinc phosphate for example. These resins impart exceptional properties to the polychloroprene adhesives in respect to high heat resistance.

There can be used as little as 0.3 mole of formaldehyde per mole of alkyl phenol or the like. Frequently there is eme.g. alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. alkaline earth metal oxides and hydroxides. e.g. calcium oxide. calcium hydroxide. barium hydroxide and magnesium oxide. alkali carbonates. e.g. sodium carbonate and potassium carbonate. ammonium hydroxide. quaternary ammonium hydroxides. anion exchange resins. basic amines. e.g. triethanolamine.

The alkaline material can be neutralized with any conventional acid. e.g. hydrochloric acid. hydrobromic acid. oxalic acid. chloroacetic acid. phosphoric acid. etc.

The order of reacting the phenol. formaldehyde and zinc resinate or. other source of zinc is not critical. The zinc resinate 'or other source of zinc is normally used in an amount of 5 to 75%. frequently 5 to 35%and most often in an amount of 7.6 to 18% based on the final resin. As little as 1% of zinc compound can be employed. The reaction with the zinc resinate or other source of zinc is carried out with heat usually terminating at I50 to 250 C. although other 7 temperatures. can be used. When rosin is employed. it is usually used in an amount of 20 to 45% of the phenols employed but can be used in lesser amounts down to zero.

The alkaline catalyzed phenol-formaldehyde resin is preferably from 60 to of the total final resin.

Unless otherwise indicated. all parts and percentages are by weight.

While in the specific examples there was employed Neoprene AC (a nonsulfur modified chloroprene polymer stabilized with thiuram disulfide) there can be used other commercially available neoprenes such as Neoprene Type CG. Neoprene Type AD. Neoprene Type ON. and Ncoprene W. These various neoprenes are described in Kell Patent 3242.1 13.

There is employed 5 to 200 parts of the zinc resinate or other zinc compound reacted phenolic resin per parts of neoprene (polychloroprene).

The adhesive cement also contains a volatile organic solvent. This solvent can be toluene. ethyl acetate. trichloroethylene. methyl ethyl ketone. hexane. acetone. benzene or mixtures of these materials. Suitable solvent mixtures for example are shown in the Garrett patent 3.185.658 column 3. lines 3-39.

There can also be included in the adhesive cement conventional neoprene additives such as zinc oxide and magnesium oxide and antioxidants such as Zalba-special (a hindered phenol composition coming within the disclosure and claims of US. Patent No. 2.999.841 and made of 45% hindered phenol. 45% sorbitol and 10% Microcell B (calcium silicate) the hindered phenol being largely 2.6-di-t-butyl-p-phenyl phenol with smaller amounts of isomeric impurities and a small amount of 2.46-tri-t-butyl phenyl phenol) and other hindered phenols. e.g. 2.6-di-t-butyl-4 phenylphenol. methyl-o-t.-butyl methylene bis-phenol. 2.2'-methylenebis (4-methyl-6-t-butyl phenol). as well as amines. e.g. Neozone D (N-phenyl-B-naphthylamine) N-phenyl a-naphthylamine. etc.

EXAMPLE 1 900 grams of xylene. 15.6 grams of Bisphenol A. 283

grams of p-phenylphenol. 500 yams of p-t-butyl phenol. 50

grams of methanol and 529 grams of 37% aqueous formaldehyde were loaded into'a'glass flask set up for atmospheric reflux. The mixture was heated to 55 C.. then 75 grams of 50% aqueous sodium hydroxide was added and the batch was brought to reflux and held for 45 minutes. The reaction mixture was then cooled by adding 500 grams of water. The pH of the resin was then brought to 1 by the addition of 165-170 grams of 20% aqueous hydrochloric acid. The neutralized condensate was agitated for a while. then the layers were allowed to separate. The water layer was decanted and the resin was washed twice more with 500 parts each time of water to remove sodium chloride.

The flask was then set up for distillation and there were. added 285 grams of wood rosin and 9 grams of 85% phosphoric acid. The resin was distilled at atmospheric pressure to approximately 150 C. There were then added grams of Unirez 1028 (zinc resinate) and distillation was continued to 215 C. Full vacuum was applied and the distillation was continued to 225 C. The resin was then poured out of the flask to cool. The yield was 1260 grams. M.P. 315 F.. molecular weight. 1705. V

This thermoplastic resin developed in neoprene adhesives extraordinary resistance to peel and shear stresses at elevated temperatures. It alsoimparted phase resistance to neoprene adhesives compounded therefrom. I

EXAMPLE 2 This adhesive formulation was prepared to evaluate the product of example 1.

'Part A Neoprene AC I parts Zinc Oxide Magnesium Oxide 4 Zalba Special 2 The above ingredients were mixed on a cold roll mill. then the compounded elastomer was cut into chunks and dissolved in 335 parts of toluene.

Part B Resin produced in example I 45.0 parts Magnesium Oxide 4.5 Water 2.0 Toluene 47.5

The above ingredients were placed in a pint can and rolled overnight at room temperature to prereact the resin.

Parts A and B were then blended together to form the finished adhesive composition.

The adhesive was then tested for shear strength when bonding cotton duck to an alkyd painted panel. The shear strength was tested at room temperature. l58 F. and 250 F.

Below are recorded the maximum shear values obtained. along with a control adhesive which contains SP-l34. a conventional heat reactive phenolic resin made from p-tbutylphenol. Bisphenol A and formaldehyde (M.P. Cap. 160 F.) compounded exactly as the above adhesive.

Resin of Condition SP-l54. Example I.

. Pli psi Room Temp. I05 I I5 I58 F. 5 54 250 F. I2 49 EXAMPLE 3 l A mixture of xylene 900 g.. Bisphenol A 15.6 g.. p-phenylphenol 283 g.. p-t-butylphenol 500 g.. 37% formaldehyde 480 g. and methanol 50 g. was brought to 55' C. Then 75 g of 50% sodium hydroxide was added. The temperature was brought to reflux and held for V: hour. The batch was then neutralized with I68 g. hydrochloric acid. The resin was then washed twice with water as in example I.

Three grams of 85% phosphoric acid. and three hundred neutralized. with 59.4 gms. of 20% hydrochloric acid. The resin was then washed twice with water. Eighty grams of wood rosin was then added and the mixture heated to 150 C. under atmospheric distillation. Thirty-eight grams of Zinc Resinate (Unirez- 1028) was added and heating was continued to l90 C. The resin was then poured into a pan to cool. Yield= 410 g.. Melting Point (Cap) 260 F.

EXAMPLE 6 A mixture of 300 g. of xylene. 5 g. of Bisphenol A. 70 g.

, of p-chlorophenol. I66 g. of p-t-butylphenol. l3 g. of methgrams of wood rosin were added and the mixture was heated to I C. while atmospherically distilling off volatiles. Zinc resinate ll4 g. was then added and the mixture was brought to I90 C.. held i4 hour. then poured into a pan to cool. yielding I269 g. of a homogeneous resin. M.P. Cap. 300 F.

EXAMPLE 4 EXAMPLE 5 A mixture of 300 g. of xylene. 5.6 g. of Bisphenol A. US

g. of alpha methylstyryl phenol. I66 g. of p-t-butylphenol, I6 g. of methanol. I40 g. of 37% formaldehyde was heated -to C. 27 g. of 50% aqueous sodium hydroxide was added and the mixture was heated to reflux. The reaction was maintained at reflux for 40 minutes. The resin was then applied to I44 C. under distillation conditions. Zinc Resianol. I60 g. of 37% uninhibited formaldehyde was heated to 55 C.. then 25 g. of 50% sodium hydroxide was added.

The temperature was brought to reflux and held at this temperature for 50 minutes. The mixture was neutralized with 77 g. of 20% hydrochloric acid. The resin was then washed twice with water. One gram of phosphoric acid and g. of wood rosin were added and the temperature was brought to l56 C. Thirty-eight g. of zinc resinate was then added and the temperature was brought to 205 C. The resin was then poured into a pan to cool. Yield=379 g.. Melting Point (Cap) 304 F. I

EXAMPLE 1 A mixture of 300 g. of xylene. 94 g. of p-phcnyl-phenol. I66 g. of p-t-butylphenol. I3 g. of methanol. I60 g. of 37% formaldehyde was heated to 55 C. then 25 g of sodium hydroxide was added. The temperature was brought to reflux and held for 38 minutes. The reaction product was then neutralized with 78.l g. of 20% hydrochloric acid. The resin was then washed twice with water.

One gram of 85% phosphoric acid and I07 g. wood rosin was added and the mixture was distilled to C. Thirtyeightg. of Unirez I028 (Zinc Resinate) was added and the reaction was continued to 205 C. The resin was then poured into a pan to cool. Yield-417 g.. M.P. (Cap)= 308 F.

EXAMPLE 8 A mixture of 900 g. of xylene. I5.6 g. of Bisphenol A. 283 g. of p-phenylphenol. 500 g. of p-t-butylphenol. 50 g. of methanol. 496 g. of 37% formaldehyde was heated to 55 C. then 75g. of 50% sodium hydroxide was added and the mixture was brought to reflux. Reflux was held for 45 minutes. The mixture was then neutralized with I84 g. of 20% hydrochloric acid. The resin was washed twice with water. Nine g. of 85% phosphoric acid was added and heat was nate (Unirez l0l4). H4 3. was added and distillation was continued to 187 C. The resin was then poured into a pan to cool. Yield-= 1047 g. M.P. (Cap)= 290 F.

The resins set forth in examples 3-8 were employed in place of the resin of example I in the adhesive formula of example 2 with the following results in the shear strength test.

250 F. Shear Example Strength 57 psi 63 psi 34 psi 35 psi 53 psi 59 psi It can be seen that the resins of the present invenlionare much superior in their ability to promote elevated temperature adhesion in polychloroprene adhesives than conventional adhesive resins such as SP-I34.

5 EXAMPLE 9 To show that a simple mixture of zinc resinate and alkyl phenoformaldehyde resin did not exhibit the high temperature adhesion exhibited by the resins of the present invention in chloroprene adhesives the following experiment was carried out.

A mixture of xylene 900 g. Bisphenol A. 15.6 g.. p-phenylphenol 283 g.. p-t-butylphenol. 500 g.. methanol 50 g. 37% uninhibited formaldehyde. 480 g. was heated to-52 C.. then 75 g. of 50% sodium hydroxide was added. The temperature was brought to reflux. The temperature was held for approximately one hour. The resin was then neutralized with I87 g. of 20% hydrochloric acid. The resin was washed twice. Four g. of 85% phosphoric acid was added. The temperature was then brought to 165 C. and the resin was poured into a pan to cool. Yield= i330 g.. M.P. (Cap)=200 F.

The following pulverized mixtures were prepared by grinding in a mortar:

Component 9(a) 90!) (C) 9(6) Unlrez 1028 parts l4 pans 0 parts I0 parts Wood rosin 0 28 2! 0 Resin olExample 9 I00 I00 7 I00 I00 250' F. Shear Example Strength 0) I2 Psi 90:) 22 psi 9(c) ll psi 9(d) I0 psi It will be observed that the 250 F. adhesion values are very poor compared to the reacted materials employed in the present invention.

EXAMPLE I0 900 grams of xylene. 283 grams (L66 moles) of p-phenylphenol. 15.6 grams (0.066 mole or 0.l32 equivalent) of Bisphenol A. 500 grams (3.33 mole) of p-t-butylphenol. 50 grams of methanol and 165 grams (2 moles) of 37% aqueous formaldehyde were loaded into 'a liter flask set up for reflux. At. 50 C. 25 grams of 50% aqueous sodium hydroxide were added. the temperature was then brought to reflux and held for 30 minutes. Then 350 grams of water were added and next 50 ml. of aqueous HCI to neutralize the sodium hydroxide. The batch was brought to 80 C. and 900 grams of Unirez 1028 added. The resin was then distilled at 23 inches of vacuum to I90 C. and poured. The yield was 1686 grams. M.P. (Capillary) I70 F.

EXAMPLE I I 900 grams of xylene. 283 grams of p-phenylphenol. l5.6 grams of Bisphenol A. 500 grams of p-t-butylphenol, 50 grams of methanol and 331 grams (4.0 moles) of 37% aqueous formaldehyde were loaded into a 5 liter flask set up for reflux. At 45' C. grams of 50% aqueous sodium hy' droxide. were added. the temperature was then brought to reflux and held for I0 minutes. Then 350 grams of water were added as wellas 50 ml. of 20% aqueous HCl. The resin was allowed to settle, the water layer siphoned off and 2100 grams of Unirez I028 were added at I40 C. during an atmospheric distillation. The temperature was brought to 180 C. and then 20 inches of vacuum was applied and distillation was continued to 210 C. The resin was then poured into a pan to cool. The yield was 2826 grams. M.P. (Capillary) 250 F.

EXAMPLE 12 The resins prepared in examples l0 and l l were employed in place of the resin of example I and the neoprene adhesive formula of example 2 with the following results in the shear strength test.

250 F. Shear Example Strength I0 28 psi ll 35 psi Thus they had shear strength properties similar to those of examples 5 and 6 and were superior to the conventional adhesive resins such as SP-I34.

EXAMPLES I3-l6 The formulations employed were as follows. The amounts were in grams.

Procedure Materials A-F were loaded into a 5 liter flask set up for reflux. The temperature was brought to 50 C. Then G was added and the temperature brought to reflux and held for one hour. The batch was cooled to C. and aciditied with No a pH of 3.0. The mixture was agitated for 0.5 hour and the two layers were allowed to separate. The aqueous phase was decanted. The resin phase was washed first with J and then with K. Material L was added and the resin was distilled to I50 C. Material M was then added and distillation was continued to the following temperatures. The resins were then poured into a pan to cool.

The resins prepared in examples 3-l6 were-employed in place of the resin of example I in the neoprene adhesive formula of example 2 with the foliowingresults in the shear strength test.

250%. Shear Example Strength 59 psi 2| psi 33 psi 32 psi ZZZ EXAMPLE l8 This example illustrates the use of another zinc compound to replace zinc resinate.

Formulation Amount A Xylene 900 grams B p-phenylphenol 283 g.

C Bisphenol A l5.6 g.

D Methanol 50 g.

E p-t-butylphenol 500 g.

F 37% formaldehyde 480 g.

G 5096 sodium hydroxide 75 g.

H Water 350 g.

l 20% "Cl 155 m 1 Water 500 g.

X Water 500 g.

M Wood Rosin ill I.

N Zinc carbonate (basic) 30 g ilocoi ZMOHM Materials A-F were loaded into a liter flask set up for reflux. The temperature was brought to 50 C. and G was added. The temperature was brought to reflux and held for 0.5 hour. Material H and l were added and the temperature then brought to 80 C. The mixture was agitated for 0.5 hour and then the aqueous phase was decanted. The

resin solution was washed first with material .l and then with material K. The resin was then acidified with L and M was added. The resin was distilled atmospherically to C. and then N was added and distillation was continued to 220' C. and held for 20 minutes.

The batch was then poured into a pan to cool. The product had a melting point (capillary) of 290 F. and a molecular weight of 1155. In the shear strength test at 250' F. in the neoprene formulation of example 2 the adhesive had a 36 psi tensile shear value. This was much superior to a conventional phenolic beat reactive resin whichu'sually' 5. An adhesive composition according to claim 4 wherein the phenol formaldehyde resin contains at least 0.7 molc of" formaldehyde per mole of phenol and the zinc resinzrte is used in an amount of 5 to 35% based on the final resin.

6. An adhesive composition according "to claim 5 wherein the phenol formaldehyde resin is a para alkylphenol formaldehyde resin having a part of the alkylphenol replaced by a member of the group consisting of arylphenols. chlorophenol and 2.2-bis-(4-hydroxyphenol) propane wherein the heat reaction in preparing the zinc resinate-phenol formaldehyde product was terminated at a temperature between l C. and 250 C. i

7. An adhesive composition according to claim 6 including rosin.

8. An adhesive composition according to claim 5 wherein the phenol formaldehyde resin contains at least 0.3 mole of formaldehyde per mole of phenol and the zinc resinate is used in an amount of 5 to 75% based on the final resin.

9. An adhesive composition according to claim 8 wherein the phenol formaldehyde resin is a p-alkylphenol formaldehyde resin having 2 to 70% of. the alkylphenol replaced by a member of the group consisting of arylphenols. chlorophenol and 2.2 bis-(4'-hydroxyphenyl) propane and wherein the heat reaction in preparing the zinc resinutc-phenol formaldehyde product was terminated at a temperature between l50 C. and 300C.

10. An adhesive composition according to claim 9 including rosin.

II. An adhesive composition comprising a polymer of chloroprene and the heat reaction product of a zinc compound selectedfrom the group consisting of zinc resinate.

zinc oxide. zinc carbonate. zinc borate. zinc salicylate and zinc phosphate. and an alkaline condensate alkyl or aryl substituted phenolformaldehyde resin.

12. An adhesive composition according to claim II wherein the zinc compound is a zinc compound other than zinc resinate. I I.

13. An adhesive composition according to claim It where- -in the zinc compound is selected from the group consisting of zinc oxide. zinc borate.'zinc phosphate. zinc salicylate and basic zinc carbonate.

14. An adhesive composition according to claim it wherein the phenol is a para alkyl phenol.

15. An adhesive composition according to claim 14 wherein the alkyl group has 3 to 6 carbon atoms.

16. An adhesive composition according to claim it comprising 100 parts of the chloroprene polymer and 5 to 200 pound is used in an amount of 0.5 to 75% based on the final resin. g

18. An adhesive composition according to claim 17 where in the zinc compound is selected from the group consisting of zinc oxide. zinc borate. zinc phosphate. zinc salicylate and zinc carbonate.

19. A composition according to claim 18 including rosin in an amount of 20 to 45% of the phenols employed. 1

cases UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N0- Dated 2Q Inventor(s) Kenneth C. Petersen and Thomas M. Galkiewicz It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Delete the drawing Col. 6 (in Example 17), line 22, "3-16" should be -"'l3-l6--.

Signed and sealed this 3rd day of July 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. Rene Tegtmeyer Attesting Officer Acting Commissioner of Patents JRM PO-1 50I1 USCOMM-DC 60376-P69 Q U 5 GOVERNMENT PRINTING OFFICE 9G9 O355-334 

2. The method of claim 1 including the steps of applying a secondary fluid pressure to at least partially sever the parison from the extrusion outlet after said series of varied fluid pressures have been applied and immediately thereafter dissipating said secondary fluid pressure to permit extrusion of a subsequent parison in a substantially uninterrupted manner.
 3. The method of claim 1 wherein the series of varied fluid pressures applied during said extrusion is between 3 to
 100. 4. The process of claim 1 wherein said extrusion of the parison between the die casing and the pin continues during observation of the pin movement.
 5. The process of claim 1 including the steps of generating a continuous signal of varying electrical intensity and continuously converting said continuous electrical signal to said series of varying fluid pressures.
 6. The process of claim 5 wherein said continuous signal of varying electrical intensity is repeatedly generated in a substantially uninterrupted manner during extrusion of said parison. 